JP5941606B2 - High PUFA oil composition - Google Patents

Description

  The present invention relates to non-cured or partially cured non-animal oils having low levels of trans-fatty acids and improved taste and properties particularly suitable for food applications and methods for their preparation.

  As consumers become aware of the health effects of lipid nutrients, consumption of high levels of unsaturated and polyunsaturated fats and low levels of trans-fat oils is desired.

  Oils containing long chain polyunsaturated fatty acids (PUFA) can be used as food material. Important PUFAs are docosahexaenoic acid (DHA), eicosapentaenoic acid (EPA), alpha-linolenic acid (ALA), gamma-linolenic acid (GLA), docosapentaenoic acid (DPA), arachidonic acid (all-c / s -5,8,11,14-eicosatetraenoic acid; AA) and stearidonic acid (c / s-6,9,12,15-octadecatetraenoic acid; SDA). Many of these PUFAs are found in marine oils and plant seeds. PUFAs are important components of phospholipids found in the plasma membrane of cells and are precursors of other molecules important in humans and animals, including prostacyclin, leukotrienes and prostaglandins. In addition, PUFAs are essential for proper development, particularly infant brain development, and tissue formation and repair.

  PUFAs can be extracted from natural sources or synthesized by various organisms. However, there are several problems with the commercial production of PUFAs from natural sources. Natural sources such as animals and plants tend to have very heterogeneous oil compositions. Oils obtained from these sources require significant refining in order to separate one or more desired PUFAs or produce an oil enriched with one or more PUFAs. Fish oils containing large amounts of EPA and DHA have an unpleasant taste and odor and are therefore undesirable as food ingredients and supplements. Further, in some cases, fish oil capsules contain low levels of desired ingredients and other ingredients such as impurities at undesirable levels.

  PUFAs are considered useful for nutritional, pharmaceutical, industrial and other purposes. Therefore, there is an interest in extracting oils with high levels of PUFAs from genetically modified seeds; these seeds have been modified to contain high levels of SDA compared to naturally occurring ones. .

  One embodiment of the present invention is at least 0.4% by weight of at least one polyunsaturated having 4 or more carbon-carbon double bonds, based on the total weight of fatty acids or derivatives thereof in the composition. Directed to an oil composition comprising a fatty acid or derivative thereof, said composition having a peroxide value of less than about 1 meq / kg and derived from a source other than marine oil; anisidine value of less than about 3 Has and is derived from sources other than marine oils; has at least one additional polyunsaturated fatty acid or derivative thereof having 4 or more carbon-carbon double bonds and an anisidine value of less than about 3; Either about 400 ppm tocopherol; or less than 1% by weight of trans-fatty acids.

  Another embodiment of the present invention is at least one polyunsaturation having 4 or more carbon-carbon double bonds, based on the total weight of fatty acids or their derivatives in the composition, at least 0.4% by weight. Directed to an oil composition comprising a fatty acid or a derivative thereof, said composition comprising Arabidopsis, canola, carrot, coconut, corn, cotton, flax, linseed, maize ), Palm kernel, peanut, potato, rapeseed, safflower, soybean, sunflower, tobacco, and mixtures thereof.

  Yet another aspect of the present invention is directed to a method of maintaining the storage stability of an oil during shipping or storage, said method comprising at least one month of the present invention at a temperature in the range of about 4 to about 45 ° C. Storing the oil in a container, wherein the oil has an anisidine value of less than 3 after storage.

  Yet another aspect of the present invention is directed to a method of maintaining the storage stability of an oil during shipping or storage, said method comprising at least one month of the present invention at a temperature in the range of about 4 to about 45 ° C. Including storing the oil in a container, wherein the absolute change in the anisidine value during storage does not exceed about 20.

  Yet another aspect of the present invention is directed to a method for maintaining the storage stability of oil during shipping or storage, said method comprising storing the oil of the present invention in a container and freezing said container.

  Yet another aspect of the invention is directed to a method of maintaining the storage stability of an oil during shipping or storage, said method comprising encapsulating the oil of the invention in an encapsulant.

  Yet another aspect of the invention is directed to an edible composition, beverage, nutritional supplement, or cooking oil comprising the oil of the invention.

  FIG. 1A is a graph of peroxide value (PV) versus time for an oil composition containing 20 wt% stearidonic acid (SDA) and various stabilizers added. The graph of FIG. 1 shows the results of an accelerated aging test performed at 55 ° C.

  FIG. 1B is a graph of anisidine value (AV) versus time for an oil composition containing 20 wt% stearidonic acid (SDA) and various added stabilizers. The graph of FIG. 1 shows the results of an accelerated aging test performed at 55 ° C.

  FIG. 2A is a graph of PV versus time for a 20% SDA, 4% SDA blend, 20% SDA containing citric acid and a control soybean oil composition. The graph of FIG. 2 shows the results of an accelerated aging test performed at 55 ° C.

  FIG. 2B is a graph of AV versus time for a 20% SDA, 4% SDA blend, citric acid with 20% SDA and a control soybean oil composition. The graph of FIG. 2 shows the results of an accelerated aging test performed at 55 ° C.

  FIG. 3A is a graph of PV versus time for a 20% SDA, 4% SDA blend, 20% SDA containing citric acid and a control soybean oil composition. The graph of FIG. 3 shows the results of a room temperature aging test performed at 25 ° C.

  FIG. 3B is a graph of AV versus time for a 20% SDA, 4% SDA blend, citric acid with 20% SDA and a control soybean oil composition. The graph of FIG. 3 shows the results of a room temperature aging test performed at 25 ° C.

  FIG. 4 is a graph of AV versus time for 20% SDA, citric acid with 20% SDA, commercial fish oil, and a bioequivalent SDA blend oil composition. The graph of FIG. 4 shows the results of an accelerated aging test performed at 55 ° C.

  FIG. 5 is a graph of peroxide value (PV) versus time for a 20% SDA oil composition containing 200 ppm ascorbyl palmitate and 0, 30, 60, and 120 ppm propyl gallate. FIG. 5 shows the results of an accelerated aging test performed at 60 ° C. using thin film IR.

  FIG. 6A shows (i) ascorbyl palmitate (AP) and TBHQ, (ii) citric acid (CA) and ascorbyl palmitate (AP), and (iii) citric acid (CA), TBHQ, and ascorbyl palmitate ( 2 is a graph of peroxide value (PV) versus time for a 20% SDA oil composition containing (AP).

  FIG. 6B shows (i) ascorbyl palmitate (AP) and TBHQ, (ii) citric acid (CA) and ascorbyl palmitate (AP), and (iii) citric acid (CA), TBHQ, and ascorbyl palmitate ( FIG. 2 is a graph of anisidine value (AV) versus time for a 20% SDA oil composition containing (AP).

The oils of the present invention have improved stability with respect to taste and odor and low levels of trans-fatty acids. In one embodiment, certain oils of the present invention can be used as food ingredients because of the health benefits of consumption of higher unsaturated fats. It is known that consumption of saturated fats has a negative impact on cardiovascular health. However, consumption of fatty acids having 4 or more double bonds is desirable. Due to the high level of unsaturation (4 or more double bonds), certain oils of the present invention are less stable compared to oils with low levels of unsaturation (less than 4 double bonds). Certain oils of the present invention with low stability will cause fatty acid degradation reactions, producing undesirable peroxides and hydroperoxides. Subsequent decomposition of these oxidation products produces volatile and non-volatile aldehydes and / or ketones. The non-volatile component catalyzes further oxidation of the oil, and the volatile component generates an undesirable taste and odor.

  One embodiment of the present invention is a polyunsaturated fatty acid having 4 or more carbon-carbon double bonds or a derivative thereof (eg, SDA) of at least about 0.4% by weight, based on the total weight of fatty acids in the composition ), The composition having an anisidine value of less than about 3 and derived from sources other than marine oils.

  The method of preparing the oil of the present invention includes the speed of the oxidation process, including seed storage and treatment, the concentration of oxidants (eg, oxygen, chlorophyll and metals), the temperature of the system, exposure of seed meat or oil, naturally occurring Developed by optimizing many factors that affect stabilizers or antioxidants (eg tocopherols) and other concentrations. The correlation of these factors is complex. This method imparts improved seed oil stability to the oil composition, as characterized by sensory and taste data, compared to seed oil prepared by conventional methods.

I. Oil composition A.1. Oxidative stability The various oil compositions of the present invention are oils extracted from a variety of non-animal sources. Advantageously, the compositions of the present invention have better stability than known oil compositions.

  In general, the stability of oils is important in determining their use. For example, it is known that oils with high concentrations of omega-3 fatty acids provide good health benefits and can be advantageously used as food ingredients. In particular, omega-3 fatty acids are known to benefit cardiovascular health, cognitive development, infant nutrition and help in preventing cancer, rheumatism and osteoarthritis, and mental illness. In recent years, the main source of omega-3 fatty acids is fish oil. Omega-3 fatty acids are more reactive because they have more double bonds in the fatty acid (3 or more). Thus, because of the taste and smell of omega-3 oils processed from fish oil, omega for use as a food ingredient (eg, added to bread, crackers, salad dressings, mayonnaise, margarines and spreads, pet food, beverages, etc.) -3 The goal is to find a good source of oil. Accordingly, aspects of the present invention provide a source of omega-3 fatty acids that have advantageous taste and olfactory characteristics for use as food ingredients and / or potential health benefit products.

  In general, oils having a large number of olefin functional groups have a higher oxidation rate than oils having a small number of olefin functional groups. The reaction scheme describing the oxidation of unsaturated fatty acids (UFA) involves a radical chain reaction characterized by initiation, growth and termination reactions. An example of the initiation reaction makes it essential to extract a hydrogen atom from a fatty acid to produce a fatty acid having a free radical. UFAs with more than one double bond and allylic carbon are more reactive than polyunsaturated fatty acids with other configurations. This is because allyl hydrogen is easier to extract and allyl radicals are more stable than other radicals. During growth, UFA with an allyl radical reacts with molecular oxygen to produce a peroxide compound. Peroxide compounds react with other UFAs to abstract hydrogen atoms and produce other fatty acid radicals during the growth phase. Alternatively, allyl radicals react with other radicals to produce inactive products at the termination stage.

  Factors affecting the oxidation of oils having one or more unsaturated fatty acids include the concentration of the agent that initiates the abstraction of hydrogen atoms from UFA, the concentration of molecular oxygen, compounds that react with radicals to produce stable products (eg, , The concentration of stabilizers and other radicals that cause termination) and the correlation with various other reaction conditions that moderate the reaction rate of the oxidation reaction. Molecular oxygen is one of the most important species needed to sustain the production of peroxide compounds from UFA, and the above factors have a complex relationship.

  In general, the relationship between the concentration of oxidant that initiates the generation of radical species and the stability of the highly unsaturated oil depends on the particular oxidant and the initiation reaction that occurs. When molecular oxygen is incorporated at the growth stage of the total oxidation reaction scheme, the relationship between molecular oxygen concentration and UFA oxidation rate is approximately linear. However, molecular oxygen can participate in other types of reactions in the total oxidation reaction scheme. For example, the proposed initiation mechanism is hydrogen abstraction from UFA with trace amounts of metal ions. In addition, UV light and temperature have been found to increase the rate of direct attack by oxygen on UFA. It is also believed that UFA is oxidized by hydrogen peroxide generated from metal catalyzed water splitting or by reaction with trace amounts of singlet oxygen. All of these reactions are plausible and lead to a complex relationship of growth factors, stability and oil quality cycle, as described below.

  The relationship between stabilizer concentration and the rate of UFA oxidation depends on the particular stabilizer, but this relationship is complicated by the presence of more than one stabilizer. The addition of multiple stabilizers acts to stabilize each other, and is more effective with stopped free radicals than a single stabilizer. For example, this stabilizer combination has an additional effect, or together, is more effective than achieved with the same amount of either stabilizer.

  Despite the complexity of UFA oxidation, the stability of compositions containing UFA can be quantified by measuring certain compounds produced in various oxidation reactions. For example, the peroxide value (PV) is the concentration of the peroxide compound in the oil measured in meq / kg. Peroxide compounds are produced during UFA oxidation, thus, the higher the PV value, the more UFA oxidation has occurred. Furthermore, the PV of the oil can be minimized by reducing peroxide production or by removing / decomposing peroxide or hydroperoxide present in the oil. PV can be minimized with various technologies, including but not limited to processing protocols.

  Another type of measurement used to assess the post-oxidation stress experienced by the oil is called the oil's anisidine value (AV). AV indicates the amount of oxidation experienced before the measurement and is a measure of the concentration of the secondary oxide. Oil AV is a measure of the amount of non-volatile aldehydes and / or ketones in the oil. An oil's AV is a measure of its oxidation history as it indicates the amount of non-volatile aldehydes and / or ketones (typically unitless) in the oil. Aldehydes and ketones are produced by the differentiation of peroxide or hydroperoxide species, which are the primary oxides of olefinic functional groups on fatty acids. Methods for measuring PV or AV of oil are well known in the art and include AOCSCd8-53 and AOCSCd18-90, respectively.

  Minimizing the amount of oxidation indicated by PV and AV has a significant impact when assessing the oxidative stability of oils. For example, peroxides and hydroperoxides readily decompose to produce odorless products and aldehydes and ketones that act as catalysts for further oxidative degradation of the oil.

  Another measure of fatty acid oxidation is the total oxidation or totox value. This totox value combines the primary (PV) and secondary (AV) oxidation products and is calculated from the formula: 2PV + AV.

A method for quantifying oxidative stability is the oxidative stability index (OSI); one method of measuring OSI is AOCSCd12b-92. The value for OSI is the time before the change in the maximum rate of oxidation (usually the unit of time) (generally referred to as the growth phase of the oxidation reaction); this time is usually referred to as the induction phase.
There are a number of factors that affect the OSI value of an oil, but this value is useful with other measures that give a semi-quantitative prediction of oil stability.

  Another way to quantify the oxidative stability of oil is to use standardized sensory evaluation. In general, standardized sensory evaluation assesses the odor, taste, and feel characteristics and flavor of an oil, as well as the characteristics of a food containing that oil, depending on whether the food is fried or mixed with the food. . For example, many characteristics of oils and foods that have been cooked with or containing the oils can be evaluated. In addition, trained panelists can select from a variety of numerical criteria to assess the tolerance of the oil being tested in the sensory evaluation. One skilled in the art can design an appropriate sensory evaluation. Sensory evaluation results determine oil tolerance for specific uses and are an important measure of oil stability.

  Specific odor and taste indicators for oil are: bacony, beans, bitter, bland, burnt, cardboardy, corny, fried ( deep fried), fishy, fruity, grassy, green, hay, heated oil, hully grain, hydrogenated oil ), Lard, light struck oil, melon, metal, metallic, musty, nutty, overheated oil, oxidized , Pointy, paraffin oil, peanut oil, pecan oil, petroleum, phenolic, pine oil, plastic, swamp (pondy), pumpkin (pumpkin), rot (rancid), raw (raw), reverted oil, rubber (rubbery), soap (soapy), sour (sour), sulfur (sulfu) r), including sunflower seed shell, watermelon, waxy, weed and woody. Typically, oils with more than 4 double bonds are characterized by a fish or swamp odor. One embodiment of the present invention is to produce an oil having more than 4 double bonds that is tasteless and odorless at the time of manufacture. Another embodiment of the present invention is to allow these oils to maintain a tasteless and odorless sensory characteristic even when stored for several months.

B. Oil compositions comprising fatty acids having 4 or more double bonds There are two main families of polyunsaturated fatty acids. Specifically, omega-3 and omega-6 fatty acids. Humans synthesize omega-6 and omega-3 polyunsaturated fatty acids from the so-called essential fatty acids, linoleic acid (LA; C18: 2ω6) and α-linolenic acid (ALA; C18: 3ω3) via the Δ ⁶ -desaturation pathway . LA is produced from oleic acid (C18: 1ω9) by Δ ¹² -desaturase. LA is in turn converted to γ-linolenic acid (GLA; C18: 3ω6) or ω6-eicosadienoic acid (EDA) by Δ ⁶ -desaturase or elongase. Each of GLA and EDA is then converted to dihomo-γ-linolenic acid (DGLA; C20: 3) by elongase or Δ ⁸ desaturase, respectively. DGLA is arachidonic acid (AA; C20: 4ω6) generates, is catalyzed by the delta ⁵ desaturase. AA, in turn, eicosapentaenoic acid by delta ¹⁷ desaturase (EPA; C20: 5ω3) is converted to. Alternatively, LA can be converted to α-linolenic acid (ALA; C18: 3ω3). ALA is in turn converted to either stearidonic acid (SDA; C18: 4ω3) or eicosatrienoic acid (EtrA; C20: 3ω3). Both SDA and EtrA are then converted to eicosatetraenoic acid (ETA; C20: 4), which is converted to EPA. EPA is then converted to docosapentaenoic acid (DPA; C22: 5) by elongase, which is then converted to docosahexaenoic acid (DHA; C22: 6) by Δ ⁴ -desaturase. However, these routes are very inefficient and consideration is needed to obtain these polyunsaturated fatty acids directly from the diet.

  In one exemplary embodiment of the present invention, the oil composition is at least about 0.4, 1, 2, 3, 4, 5, 6, based on the total weight of fatty acids or derivatives thereof of the composition. 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44 or 45% by weight or more of at least one polyanion having 4 or more carbon-carbon double bonds Contains saturated fatty acids or derivatives thereof. In one embodiment, the composition comprises at least about 400, 450, 500, 600, 700, 800, 805, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 1000, 11001200. Further comprising 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000 ppm or more tocopherol. In another embodiment, the composition comprises about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1 Has a peroxide value of less than 0.0 meq / kg and is derived from sources other than marine oils (eg, other than fish oil, seaweed oil, etc.). In another embodiment, the composition comprises about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 0.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2 It has anisidine values less than 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3.0 and is derived from sources other than marine oils. In yet another embodiment, the composition comprises about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2. 2. An anisidine value of less than 2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3.0 and 4 or more carbon-carbon double bonds At least one further polyunsaturated fatty acid or derivative thereof. In yet another embodiment, the composition further comprises less than 1 wt% trans-fatty acid.

  Furthermore, the present invention provides at least about 0.4, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 based on the total weight of fatty acids or derivatives thereof in the composition. 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 38, 39, 40, 41, 42, 43, 44 or 45 wt% or more of an oil composition comprising at least one polyunsaturated fatty acid having 4 or more carbon-carbon double bonds or a derivative thereof. The composition comprises: Arabidopsis, canola, carrot, coconut, corn, cotton, flax, linseed, maize, palm kernel, peanut, Potato and rapeseed (rapeseed ), Safflower, soybean, sunflower, and / or tobacco transgenic seed. In one embodiment, the composition comprises 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 0.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0 7.5, 8.0, 8.5, 9.0, 9.5, or 10.0 meq / kg. In another embodiment, the composition comprises 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7. It has an anisidine value of 0, 7.5, 8.0, 8.5, 9.0, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20. In another embodiment, the composition comprises 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7. 0, 7.5, 8.0, 8.5, 9.0, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, It has a totox value of 24, 25 or 26. In yet another embodiment, the composition comprises 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900. 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400 It further comprises up to 4500, 4600, 4700, 4800, 4900, or 5000 ppm or more tocopherol. Tocopherol is a naturally occurring stabilizer and includes α-tocopherol, β-tocopherol, γ-tocopherol, and δ-tocopherol. In yet another embodiment, the composition comprises 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 0.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0 , 7.5, 8.0, 8.5, 9.0, 9.5, or 10.0% by weight of trans-fatty acids. In another embodiment, the composition comprises at least about 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50% by weight γ-linolenic acid (GLA; C18: 3) or a derivative thereof.

  Representative polyunsaturated fatty acids having 3 or more double bonds or derivatives thereof are stearidonic acid (SDA; C18: 4), eicosatetraenoic acid (ETA), eicosapentaenoic acid (EPA; C20: 5 ), Docosapentaenoic acid (DPA; C22: 5), docosahexaenoic acid (DHA), and arachidonic acid (AA; C20: 4). Preferably, the polyunsaturated fatty acid or derivative thereof of the oil composition comprises at least one omega-3 or omega-6 fatty acid, preferably omega-3 stearidonic acid (SDA; C18: 4), omega-3 Eicosatetraenoic acid (ETA), omega-3 eicosapentaenoic acid (EPA; C20: 5), omega-3 docosapentaenoic acid (DPA; C22: 5), omega-3 docosahexaenoic acid (DHA; C22: 6) Or omega-6 arachidonic acid (AA; C20: 4).

  The present invention is also useful for genetically modified vegetable oils containing polyunsaturated fatty acids containing elevated levels of 3 or more carbon-carbon double bonds. For example, Arabidopsis, canola, carrot, coconut, corn, cotton, flax, linseed, corn (maize), palm kernel, peanut, potato, rapeseed , Plant seeds derived from safflower, soybean, sunflower, and / or tobacco. Representative polyunsaturated fatty acids having 3 or more double bonds or derivatives thereof include stearidonic acid (SDA; C18: 4), eicosatrienoic acid (EtrA; C20: 3), eicosatetraenoic acid (ETA). , C20: 4), eicosapentaenoic acid (EPA; C20: 5), docosapentaenoic acid (DPA; C22: 5), docosahexaenoic acid (DHA; C22: 6), gamma linolenic acid (GLA; C18: 3), Dihomogamma linolenic acid (DGLA; C20: 3) and arachidonic acid (AA; C20: 4). Preferably, the polyunsaturated fatty acid or derivative thereof of the oil composition comprises at least one omega-3 or omega-6 fatty acid, preferably omega-3 stearidonic acid (SDA; C18: 4), omega-3 Eicosatrienoic acid (EtrA; C20: 3), omega-3 eicosatetraenoic acid (ETA, C20: 4), omega-3 eicosapentaenoic acid (EPA; C20: 5), omega-3 docosapentaenoic acid ( DPA; C22: 5), omega-3 docosahexaenoic acid (DHA; C22: 6)), omega-6 gamma linolenic acid (GLA; C18: 3), omega-6 dihomogamma linolenic acid (DGLA; C20: 3) or Contains omega-6 arachidonic acid (AA; C20: 4).

  The composition of this section may further comprise γ-linolenic acid or a derivative thereof (C-γ18: 3), or DH-γ-linolenic acid (C-DH-γ20: 3) or a derivative thereof.

  As noted above, oils having a relatively high concentration of omega-3 fatty acid units are advantageous food ingredients. Using the method of the present invention, from oil seeds containing at least one polyunsaturated fatty acid or derivative thereof having 4 or more carbon-carbon double bonds, such as stearidonic acid, to the total weight of fatty acids in the composition About 0.4, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44 or 45% by weight or more The oil can be extracted in an amount greater than about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0 1.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2 Having anisidine value of less than 0,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9 or 3.0. Preferably, the extracted oil seed is a seed containing SDA in the same ratio as the oil composition with respect to the total fatty acid content. Thus, the total seed SDA content is at least about 0.4% by weight of the total fatty acid concentration. Further, throughout the method, the SDA content in the oil is at least about 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8 relative to the total weight of fatty acids in the composition. 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33 , 34, 35, 36, 37, 38, 39 or 40% by weight.

  In another embodiment, the whole seed or oil composition during or after processing is about 18, 19, 20, 21, 22, 23, 24, 25, 30 relative to the total weight of fatty acids in the composition. , 35 or 40% by weight of linoleic acid (LA; C18: 2n6) content and at least about 0.4, 5, 10, 15, 20, 25, 30, 35 relative to the total weight of fatty acids in the composition Having an SDA content of 40 or 45% by weight. Note that another polyunsaturated fatty acid or derivative thereof having 4 or more carbon-carbon double bonds may be substituted for SDA in these compositions or any other SDA composition described in this section. Should.

  Alternatively, the oil composition during or after processing has an SDA content of at least about 0.4% by weight, based on the total weight of fatty acids in the composition, and is about 0.5, 0.6, 0.0. 7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or Has AV up to 2 during or after processing. In particular embodiments, the oil composition has an SDA content of at least about 0.4% by weight relative to the total weight of fatty acids in the composition, and is about 0.1, 0.2, 0.3, Product bleach deodorant (RBD) oil composition having an AV up to 0.4 or 0.5.

  In a further embodiment, the RBD oil has an SDA content of at least about 0.4% by weight relative to the total weight of fatty acids in the composition and is at least about 0.5, 0.6, 0 at 110 ° C. .7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4 or 1.5 hours of OSI.

  Further, Section I.1. The oil composition described in B is black currant oil, borage oil, Echium oil, evening primrose oil, gooseberry oil, It can be derived from vegetable oils other than hemp oil or redcurrant oil. Moreover, the oil composition can be derived from oils other than fish oil (eg, menhaden, sardines, tuna, cod liver, mackerel, herring), seaweed oil and other marine oils. Marine microalgae (Crypthecodinium cohnii), benthic microalgae (Nitzchia sp.), Marine unicellular true-pointed algae (Nannochloropsis), Nemicula sp. (Navicula sp.), Marine diatoms (Phaedactylum), Porphyridium (Porphyridium) Seaweeds producing oils with four or more double bonds, including oils derived from Schizochytrium, including chrysophytes, crytophytes, diatoms, and vortices Contains dinoflagellates [Behrens and Kyle, 1996: J. Food Lipids, 3: 259-272]. Section I.1. The oil composition described in B is genetically modified Arabidopsis, canola, carrot, coconut, corn, cotton, flax, linseed, maize, palm kernel ( palm kernel), peanuts, potatoes, rapeseed, safflower, soybeans, sunflower, and / or tobacco. Finally, the oil composition can be an unblended oil.

As described above, humans synthesize omega-6 and omega-3 polyunsaturated fatty acids from linoleic acid and α-linolenic acid via the Δ ⁶ -desaturation pathway to yield γ-linolenic acid and stearidonic acid, respectively. . Furthermore, the fatty acid elongation and desaturation steps yield arachidonic acid, eicosapentaenoic acid, and docosahexaenoic acid. Alternative pathways for AA and EPA biosynthesis work in several organisms. Here, LA and ALA are first specifically extended to eicosadienoic acid (EDA; C20: 2ω6) and eicosatrienoic acid (EtrA; C20: 3ω3), respectively. Subsequent Δ ⁸ and Δ ⁵ desaturation of these products yields AA and EPA.

  DHA and EPA can also be synthesized from malonyl-CoA precursors by the polyketide synthase (PKS) pathway [Yazawa, Lipids (1996) 31, S297-S300].

According to a recent report, sequential transfer and expression of three genes encoding Δ ⁹ -specific elongation activity from brown algae (Isochrysis galbana) (IgASEI) [Qi et al., FEBS Lett. (2002) 510, 159-165 ] Reconstructed these Δ ⁸ -desaturation pathways for polyunsaturated fatty acid synthesis in Arabidopsis thaliana and accumulation of substantial amounts of AA and EPA in transformed plants [Qi et al., Nature Biotechnol. (2004 22, 739-745], Δ ⁸ -desaturase from Euglena gracilis (EuΔ ⁸ ) [Wallis and Browse, Arch. Biochem. Biophys. J. (1999) 365, 307-316] and oily microorganisms ( Mortierella alpina) -derived Δ ⁵ -desaturase (MortΔ ⁵ ) [Michaelson et al., J. Biol. Chem. (1998) 273, 19005-19059] has been demonstrated. Abbadi and colleagues also reported successful seed-specific production of ω3 and ω6 polyunsaturated fatty acids in transformed tobacco (Nicotiana tabacum) and linseed (Linum usitatissimum) [Plant Cell (2004) 16, 1-15]. Pereira et al. Reported a novel ω3 fatty acid desaturase involved in EPA biosynthesis [Biochem. J. (2004) 378 (665-671)]. The method and composition of the present invention are useful for extracting and / or stabilizing polyunsaturated fatty acids derived from organisms produced according to the above report.

  Some of the various oils of the present invention can be extracted from plant tissue, including plant seed tissue. Plants from which polyunsaturated fatty acids can be isolated include plants that have native levels of polyunsaturated fatty acids as well as plants that have been genetically engineered to express elevated levels of polyunsaturated fatty acids. Examples of plants with natural levels of polyunsaturated fatty acids include oil seed crops such as canola, safflower, and linseed, as well as flax, evening primrose (Oenothera biennis), Includes plants such as Borago officinalis and blackcurrant (Ribes nigrum), Trichodesma, and Echium. Certain moss, such as Physcomitrella patens, are known to naturally produce polyunsaturated fatty acids that can be extracted and purified by the methods of the present invention. As another example, the method of the present invention is described in U.S. Patent Nos. 6,677,145; 6,683,232; 6,635,451; 6,566,583; 6,459,018; WO946 / 55625; WO96 / 21022; and U.S. Patent Application Nos. 20040078845; 20030196217; 20030190733; 20030177508; 20030163845; 20030157144; 20030134400; 20030104596; 20030082754; 20020138874; and 20020108147. (E.g., Arabidopsis, canola, carrot, coconut, corn, cotton, flax, linseed, corn) (including maize, palm kernel, peanut, potato, rape seed, safflower, soybean, sunflower, tobacco, and mixtures thereof) And / or poly (from, for example, stearidonic acid, docosahexaenoic acid, eicosapentaenoic acid, gamma linolenic acid, arachidonic acid, dihomogamma linolenic acid, docosapentaenoic acid, and octadecatetraenoic acid). Useful for extraction and / or stabilization of saturated fatty acids.

  Other oil compositions can be extracted from fungi. Fungi from which polyunsaturated fatty acids can be isolated include fungi that have native levels of polyunsaturated fatty acids as well as fungi that have been genetically engineered to express elevated levels of polyunsaturated fatty acids. For example, the methods of the present invention include, for example (eg, Saccharomyces (including S. cerevisiae and S. carlsbergensis)), Candida spp. Cunninghamella spp. (Including C. elegans, C. blakesleegna, and C. echinulate), Lipomycess tarkey, Yarrowia lipolytica (Yarrowia lipolytica), Kluyveromyces spp., Hansenula spp., Aspergillus spp., Penicillium spp., Neurospora spp., Saproregnia spp. Sacrilegnia diclina, Trichoderma spp., Thamnidium elegans, Pichia spp., Pythium spp. (Including P. ultimum, P. debaryanum, P. irregulare, and P. insidiosum), Thraustochytrium aureum, and Mortierella spp. (M. elongata), M. exigua, M. hygrophila, M. lamaniana ( M. ramanniana), M. ramanniana var.angulispora, M. ramanniana var. Nana, M. alpina, M. Includes M. isabellina and M. vinacea. Fungi and / or U.S. Patent Nos. 6,677,145; 6,635,451; 6,566,583; 6,432,684; 6,410,282; 6,355,861; 6,280,982; 6,255,505; 6,136,574; 5,972,664; And US Patent Application Nos. 20040078845; 20030196217; 20030190733; 20030180898; 20030177508; 20030163845; 20030157144; 20030104596; 20030082754; 20020138874; 20020108147; and 2001004669 (these prior art are incorporated herein by reference) Of stearidonic acid, docosahexaenoic acid, eicosapentaenoic acid, gamma linolenic acid, arachidonic acid, dihomo gamma linolenic acid, docosapentaenoic acid, and octadecatetraenoic acid from recombinant fungi produced by the compositions and methods of Useful for the extraction and / or stabilization of polyunsaturated fatty acids (including enoic acids).

Yet another oil composition can be extracted from the microorganism. Microorganisms from which polyunsaturated fatty acids can be isolated include microorganisms having native levels of polyunsaturated fatty acids as well as microorganisms that have been genetically engineered to express elevated levels of polyunsaturated fatty acids. Such microorganisms include bacteria and cyanobacteria. For example, the methods of the present invention may include microorganisms (including, for example, E. coli, Cyanobacteria, Lactobacillus, and Bacillus subtilis) and / or US Pat. Nos. 6,677,145; 6,635,451; 6,566,583; 6,432,684; 5,972,664; 5,614,393; And US Patent Application Nos. 20040078845; 20030180898; 20030177508; 20030163845; 20030157144; 20030104596; 20030082754; 20020138874; 20020108147; and 20010046691 (these prior art are hereby expressly incorporated herein by reference). Poly (from stearidonic acid, docosahexaenoic acid, eicosapentaenoic acid, gamma linolenic acid, arachidonic acid, dihomo gamma linolenic acid, docosapentaenoic acid, and octadecane tetraenoic acid) produced by the composition and method Useful for unsaturated fatty acid extraction and / or stabilization.
The oil composition can be extracted from seaweed. Seaweeds from which polyunsaturated fatty acids can be isolated include seaweeds with native levels of polyunsaturated fatty acids as well as seaweeds that have been genetically engineered to express elevated levels of polyunsaturated fatty acids. Examples of seaweed that contain natural polyunsaturated fatty acids include Phaeodactylum tricornutum, Crypthecodinium cohnii, Pavlova, Isochrysis galbana, and Through (Thraustochytrium) is included. For example, the methods of the present invention can be obtained from seaweed and / or US Pat. Nos. 6,727,373; 6,566,583; 6,255,505; 6,136,574; 5,972,664; 5,968,809; 5,547,699; These prior art are expressly incorporated herein by reference and are derived from recombinant seaweed (stearidonic acid, docosahexaenoic acid, eicosapentaenoic acid, gamma linolenic acid, Useful for the extraction and / or stabilization of polyunsaturated fatty acids (including arachidonic acid, dihomogamma linolenic acid, docosapentaenoic acid, and octadecane tetraenoic acid).

C. Stabilization of high PUFA seed oil While promoting the oxidative stability of the oil composition without the addition of a stabilizing compound, the oil composition may further comprise a stabilizer. Stabilizers are generally added to the oil composition to prolong the onset and delay the onset of the growth phase. The stabilizer delays the onset of the growth phase by about 15 times or more compared to the growth phase time of the oil to which no stabilizer is added. Depending on the properties of the particular stabilizer, these compounds have different modes of action. Some stabilizers chelate metals and other catalytic species, otherwise they interact with oil triglycerides and increase the oxidation rate of the oil. Other stabilizers act as antioxidant molecules and oxidize triglyceride fatty acids to peroxides, which in turn are described in Section I.1. Oxidize with other fatty acids as detailed in A.
Typical stabilizers are 2,4,5-trihydroxybutyrophenone, 2,6-di-t-butylphenol, 3,4-dihydroxybenzoic acid, 3-t-butyl-4-hydroxyanisole, 4-hydroxy Methyl-2,6-di-t-butylphenol, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, anoxomer, ascorbic acid, ascorbyl palmitate, ascorbyl stearate, beta-apo-8 ' -Carotenic acid, Beta-Caraotent, Butylated hydroxyanisole (BHA), Butylated hydroxytoluene (BHT), Caffeic acid, Calcium ascorbate, EDTA calcium disodium salt, Canthaxanthin, Carnosol, Carvacrol, catalase, cetyl gallate, chlorogenic acid, citric acid, clove extract, coffee bean extract, acetic acid D-α -Tocopheryl, dilauryl thiodipropionate, disodium citrate, disodium EDTA, DL-α-tocopherol, DL-α-tocopheryl acetate, dodecyl gallate, dodecyl gallate, D-α-tocopherol, edetic acid, erythorbic acid , Esculetin, esculin, ethoxyquin, ethyl gallate, ethyl maltol, eucalyptus extract, ferulic acid, flavonoids (typically carbons such as C6-C3-C6) Characterized by two aromatic rings linked by a skeletal three-carbon aliphatic chain, usually condensed to form a pyran ring or rarely a furan ring), flavones (Apigenin, Chrysin), luteolin (Luteolin)), flavonols (Datiscetin), Niricetin (Nyricetin), Daemfero (Daemfero) ), Flavanones, and chalcones, flaxetin, fumaric acid, gentian extract, gluconic acid, glucose oxidase, heptylparaben, hesperetin, hydroxycinnamic acid, hydroxyglutaric acid, hydroxy Tyrosol, isopropyl citrate, lecithin, lemon juice solid, lemon juice, L-tartaric acid, lutein, lycopene, malic acid, maltol, methyl gallate, methylparaben, Morin, N-hydroxysuccinic acid, nordihydrogait Allenic acid (Nordihydroguaiaretic acid), octyl gallate, P-coumaric acid, phosphatidylcholine, phosphoric acid, P-hydroxybenzoic acid, phytic acid (inositol hexaphosphate), pimente extract, potassium bisulfite, potassium lactate, metabisulfite Potassium, potassium tartrate Sodium anhydride, propyl gallate, pyrophosphate, quercetin, rice bran extract, rosemary extract (RE), rosmarinic acid, sage extract, sesamol, Sinapic acid, sodium ascorbate, sodium ascorbate, sodium erythorbate, sodium erythorbate, sodium hypophosphate, sodium hypophosphate, sodium metabisulfite, sodium sulfite, sodium thiosulfate pentahydrate, three Sodium phosphate, soybean flour, succinic acid, sucrose, syringic acid, tartaric acid, t-butylhydroquinone (TBHQ), thymol (Thymol), tocopherol, tocopheryl acetate, tocotrienol, trans-resveratrol (trans-Resveratrol ), Tyrosol, vanillin , Wheat germ oil, zeaxanthin (zeaxanthin), alpha-terpineol (α-terpineol), and combinations thereof.

  A series of experiments were performed (see Examples 1-3) to determine the primary stabilizer or stabilizer combination for the oil composition of the present invention. These stabilizers can be selected from the group consisting of citric acid (CA), ascorbyl palmitate (AP), t-butylhydroquinone (TBHQ), propyl gallate (PG), and combinations thereof. In various preferred embodiments, the stabilizer in the oil is CA, TBHQ, and combinations thereof. In various alternative embodiments, the stabilizer in the oil is AP, PG, and combinations thereof. In other preferred embodiments, the stabilizer in the oil is

  Citric acid is added to the oil composition at a concentration of about 1 ppm to about 100 ppm; preferably about 20 ppm to about 80 ppm; more preferably about 40 ppm to about 60 ppm. Ascorbyl palmitate is added to the oil composition at a concentration from about 50 ppm to about 1000 ppm; preferably from about 100 ppm to about 750 ppm; more preferably from about 400 ppm to about 600 ppm. TBHQ is added to the oil composition at a concentration from about 10 ppm to about 500 ppm; preferably from about 50 ppm to about 200 ppm; more preferably from about 100 ppm to about 140 ppm. Propyl gallate is added to the oil composition at a concentration of about 10 ppm to about 120 ppm; preferably about 50 ppm to about 120 ppm; more preferably about 100 ppm to about 120 ppm. A combination of two or more of these stabilizers has a concentration of each stabilizer in the above range.

  In some of these experiments, an accelerated aging protocol using the novel thin film IR method was used. This method of quantifying the oxidative stability of an oil involves preparing an oil composition in an inert atmosphere; placing a layer of the oil composition on an infrared card to form a treated infrared card; Place the treated infrared card in an inert atmosphere for a sufficient time until uniform thickness; expose the infrared card with a layer of substantially uniform thickness to air; and then the infrared spectrum of the oil composition Are collected periodically. A specific embodiment of this method is described in more detail in Example 3. In various embodiments of this method, an infrared card having a substantially uniform layer thickness between about 25 ° C. and about 80 ° C., preferably about 50 ° C. to about 70 ° C. More preferably, it is stored at about 55 ° C to about 65 ° C. In other embodiments of this method, infrared spectra are collected about 12 hours to about 36 hours, preferably 24 hours apart.

  Another embodiment of the present invention is a method for reducing the anisidine value (AV) of an oil. Anisidine value is an important parameter that helps to maximize oil stability for a well formulated oil that has a high level of unsaturation and is easily oxidized in food. A new method for reducing the AV of the resulting bleached deodorized oil (RBD oil) having an AV greater than about 1 has been discovered and is described in more detail below and in Example 4. In general, the method treats an oil composition with an AV-lowering agent capable of associating with aldehydes and / or ketones in the oil composition, and then physically separates the AV-lowering agent from the oil composition. Thus, the AV-lowering agent associated with the aldehyde and / or ketone is removed from the oil composition to lower the AV. The AV-lowering agent comprises an amine bound to a support that can be separated from the oil composition.

  This method of lowering AV in RBD oil examines the unique functionality of non-volatile aldehydes and ketones remaining in RBD oil due to the decomposition of peroxides and hydroperoxides. Specifically, non-volatile aldehydes and ketones react with amines to produce substituted imines by condensation reactions (substituted imines are sometimes referred to as Schiff bases). Aldehydes and ketones can be separated from the oil composition by linking the amine to a support that can be physically separated from the oil composition. In various embodiments, the support is an insoluble support and is a macroscopic support. Once the reaction is complete, non-volatile aldehydes and ketones (now in the form of substituted imines) are bound to the insoluble support and can be physically separated from the oil by filtration.

  The above method can be used to remove aldehydes and ketones in various oils, such as vegetable oils, fish oils, mineral oils, cooking oils, frying oils, coating oils, and combinations thereof.

  In addition to various oils, the method is useful and there are a variety of amines and support materials suitable for use in the method. For example, the amine can be an aliphatic or arylamine, preferably the amine is an arylamine. Supports are polystyrene, styrene-divinylbenzene copolymer, poly (ethylene glycol) -polystyrene graft polymer, poly (ethylene glycol), polyacrylamide, polyacrylamide-PEG copolymer, silica, polysaccharides, and their You can choose from a variety of insoluble particles, including combinations. In various preferred embodiments, the support comprises polystyrene, especially polystyrene resin beads.

  This procedure can be used in any step of the oil refining process. The resin can be recycled or discarded after use. Preferably, the resin is regenerated; this is accomplished by hydrolyzing the pendant imine with acidic hot water. This regeneration allows the resin to be dried and used to remove more non-volatile aldehydes and ketones. Both generation of substituted imine and resin regeneration can be carried out in packed columns or stirred tank reactors.

D. Sensory characteristics of high PUFA seed oil In general, SDA containing the oil of the present invention has a low total impact. Thus, another aspect of the present invention provides at least about 0.4, 1, 2, 4, 6, 8, 10, 12, 14, 15, based on the total weight of fatty acids or derivatives thereof in the composition. 16, 17, 18, 19, 20% by weight or more of an oil composition comprising at least one polyunsaturated fatty acid having 4 or more carbon-carbon double bonds or a derivative thereof, wherein the composition comprises about 2 A fragrance total impact score up to .5, where the total impact is determined by standardized sensory evaluation.

  Yet another aspect is at least about 0.4, 1, 2, 4, 6, 8, 10, 12, 14, 15, 16, 17, 18 relative to the total weight of fatty acids or derivatives thereof in the composition. 19, 20% by weight or more of an oil composition comprising at least one polyunsaturated fatty acid or derivative thereof having 4 or more carbon-carbon double bonds, the composition comprising up to about 2.5 fragrances / Has a flavor total impact score, where the total impact is determined by standardized sensory evaluation.

  In addition to having a low total impact, the oils of the present invention have a low fish odor and / or swamp odor / seaweed odor. Thus, a further aspect is at least about 0.4, 1, 2, 4, 6, 8, 10, 12, 14, 15, 16, 17, 18 relative to the total weight of fatty acids or derivatives thereof in the composition. 19, 20 wt% or more of an oil composition comprising 4 or more carbon-carbon double bonds and polyunsaturated fatty acids or derivatives thereof having 18 or less carbon atoms, wherein the composition is about 0. It has a fish odor score of 5, 1, 1.5, 2, 2.5, 3, 3.5, 4, or 4.5, where the fish odor is determined by standardized sensory evaluation.

  Yet another aspect is at least about 0.4, 1, 2, 4, 6, 8, 10, 12, 14, 15, 16, 17, 18 relative to the total weight of fatty acids or derivatives thereof in the composition. 19, 20 wt% or more of an oil composition comprising 4 or more carbon-carbon double bonds and polyunsaturated fatty acids or derivatives thereof having 18 or less carbon atoms, wherein the composition is about 0. Fish / swamp combined odor scores up to 5, 1, 1.5, 2, 2.5, where the fish / swamp combined odor is determined by standardized sensory evaluation.

  Yet another aspect of the present invention is about 1, 5, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30 relative to the total weight of fatty acids or derivatives thereof in the composition. , 32, 34% by weight of an oil composition comprising a polyunsaturated fatty acid having 6 carbon-carbon double bonds and 22 carbon atoms or a derivative thereof, the composition comprising 0.5, 1 , 1.5, 2 and 2.5, where the swamp odor is determined by standardized sensory evaluation.

  Furthermore, the oil composition of the present invention has no significant time change in properties. For example, at least about 0.4, 1, 2, 4, 6, 8, 10, 12, 14, 15, 16, 17, 18, 19, 20% by weight or more based on the total weight of fatty acids in the composition An oil composition comprising at least one polyunsaturated fatty acid or derivative thereof having 4 or more carbon-carbon double bonds, said composition comprising an oil evaluated at the start and about 1 in fragrance total impact score difference Has a difference of less than about 0.5 or 1.0 when compared to the same oil stored up to two or more months.

  Another embodiment is at least about 0.4, 1, 2, 4, 6, 8, 10, 12, 14, 15, 16, 17, 18 relative to the total weight of fatty acids or derivatives thereof in the composition. 19, 20% by weight or more of an oil composition comprising at least one polyunsaturated fatty acid having 4 or more carbon-carbon double bonds or a derivative thereof, wherein the composition has an aroma / flavor total impact score difference In comparison, it has a difference of less than about 0.5 or 1.0 when compared to the oil evaluated at the start and the same oil stored up to about 1, 2, or more months.

  For each of the various embodiments described above, the oil composition may or may not be stabilized. The stabilized oil composition is described in more detail above.

II. Methods for preparing oil compositions In general, seed oil is processed using the following steps: preparation, cracking and dehulling, conditioning, milling, flaking or flaking or pressing), extracting, degumming, refining, bleaching and deodorizing. Each of these steps will be described in more detail later. The process of each step currently used in the market application is described in detail. Those skilled in the art will know that these steps may be combined, used in a different order, or modified.

  In general, the preparation steps include an initial cleaning process that removes debris that has entered during harvest and storage of stones, mud, sticks, insects, insects, metal fragments and other seeds. The foreign substances described above contain compounds that adversely affect the chemical stability of the final seed oil, and thus can affect the quality of the oil. Preferably, ripe crushed seeds with reduced levels of chlorophyll and reduced levels of free fatty acids are used.

  After the preparation step, the seeds are crushed and peeled. Crushing and peeling can be accomplished in a variety of ways well known in the art. For example, a seed cracker can be used to break up and peel the seed, which mechanically breaks the seed, pulls off the hull, and directly exposes the seed interior to air. After crushing, the hull is separated from the seed meat by a peeler. In one embodiment, the peeler separates the hull from the seed meat due to the difference in density between the hull and the seed; the hull is less dense than the seed meat. For example, suction separates the rind from crushed seed meat. Peeling reduces coarse fiber and increases the protein concentration of the extracted seed meat. If desired, after peeling, the outer skin is sieved to recover the fine particles produced during seed crushing. After collection, the fines are returned to the seed meat prior to adjustment.

  Once the seeds are crushed, oxygen exposure of the seed meat is minimized if desired to reduce oil oxidation and improve oil quality. Moreover, those skilled in the art will appreciate that the oxygen exposure minimization is performed independently at each of the oil seed processing steps subsequently disclosed.

Once the seeds are crushed and peeled, the seed meat is adjusted for easy handling before further processing. Furthermore, regulation destroys oily substances. In the sense of flaking, milling or grinding techniques, further processing can be easily done at this stage, because the seed meat is easy to handle. In general, the seed meat is dehydrated or added to a moisture level of 6-10% by weight. If the moisture is removed, this process is called toasting. If the moisture is added, this process is called cooking. Typically, depending on the direction of adjusting the moisture content of the seed meat, the seed meat is heated to 40-90 ° C. with dry or wet steam.
In some cases, the conditioning step is performed under conditions of lower temperature for high PUFA level seeds, minimizing oxygen exposure.

  Once the seed meats are adjusted, they can be ground to the desired particle size or flaked to the desired surface area. In some cases, flaking or grinding is performed under conditions that minimize oxygen exposure. Flaking or crushing is performed to increase the surface area of the seed meat and destroy oily substances, thereby allowing more efficient extraction. Many grinding techniques are suitable and are well known in the art. Considerations in selecting the grinding method and milled seed particles are not limited, but depend on the oil content in the seed and the desired extraction efficiency from the seed meat or seed. When flaking seed meat, the flakes are typically about 0.1 to about 0.5 mm thick; about 0.1 to about 0.35 mm thick; about 0.3 to about 0.5 mm thick; or About 0.2 to about 0.4 mm thick.

  If desired, the seed meat is crushed and then squeezed. Typically, seeds are squeezed when the oil content of the seed meat exceeds about 30% by weight of the seeds. However, higher or lower oil content seeds can also be squeezed. The seed meat can be squeezed with, for example, a hydraulic or mechanical screw. Typically, the seed meat is heated to less than about 55 ° C. upon input to the machine. During pressing, the oil in the seed meat is compressed through a screen, collected and filtered. This collected oil is the first squeezed oil. The pressed seed meat is called a seed cake; this seed cake contains oil and can be subjected to solvent extraction.

  After grinding, flaking or optionally pressing, the oil can be extracted from the seed meat or seed cake by contacting them with a solvent. Preferably n-hexane or iso-hexane is used in the extraction process. Typically, this solvent is degassed prior to contact with the oil. Extraction can be done in a variety of ways well known in the art. For example, the extraction can be a batch process or a continuous process, preferably a continuous countercurrent process. In the continuous countercurrent process, the solvent in contact with the seed meat squeezes the oil into the solvent, providing a more concentrated mixture (ie, solution-oil), while marc; , Solvent-solid) is contacted with the reduced concentration mixture. After extraction, the solvent is removed from the mixture as is well known in the art. For example, the solvent can be removed using distillation, rotary evaporation or a rising film evaporator and a steam stripper. After removal of the solvent, if the crude oil still contains residual solvent, it can be heated at about 95 ° C. and about 60 mm Hg.

  The processed crude oil contains a hydratable or non-hydratable phosphatide. Thus, depending on the phosphatide concentration, the crude oil is refined by adding water and heating to about 40-75 ° C. for about 5-60 minutes to remove hydratable phosphatides. If desired, phosphoric acid and / or citric acid can be added to convert non-hydratable phosphatides to hydratable phosphatides. Phosphoric acid and citric acid form a metal complex that reduces the metal ion concentration bound to the phosphatide (the metal complexed phosphatide is non-hydratable), thus converting the non-hydrated phosphatide to the hydratable phosphatide. Convert to Optionally, after heating with water, the crude essential oil and water mixture is centrifuged to separate the oil and water and the aqueous layer containing the hydratable phosphatide is removed. In general, if phosphoric acid and / or citric acid is added in the refining step, about 1% to about 5% by weight; preferably about 1% to about 2% by weight; more preferably about 1.5% by weight. % To about 2% by weight is used. This process step is optionally performed by degassing water and phosphoric acid before contacting them with oil.

  In addition, the crude oil contains free fatty acids (FFAs) that can be removed by chemical (eg, caustic) refining steps. When FFAs react with basic substances (eg caustic substances), they produce soaps that can be extracted into aqueous solutions. Thus, the crude oil is heated to about 40 to about 75 ° C. and NaOH is added with stirring and allowed to react for about 10 to 45 minutes. After this, stirring is stopped, heating is continued, the aqueous layer is removed, and the neutralized oil is treated to remove soap. The oil is treated by either washing the oil with water until the aqueous layer is at a neutral pH or treating the neutralized oil with silica or an ion exchange material. Dry the oil at about 95 ° C. and about 10 mm Hg. In some cases, the caustic solution is degassed before it contacts the oil.

Alternatively, FFA can be removed by physical purification without removing FFA from the oil by chemical purification. For example, the oil can be physically refined during deodorization. When performing physical refining, the FFA is removed from the oil by vacuum distillation at low pressure and relatively high temperature. In general, FFA has a lower molecular weight than triglyceride, and thus FFA generally has a lower boiling point, and based on this boiling point difference,
The volatiles can be separated from the triglycerides with the aid of nitrogen or steam stripping used as an azeotrope or carrier gas to drive out the deodorizer.

  Typically, when physical refining is performed rather than chemical refining, the oil processing conditions are modified to achieve similar end product specifications. For example, when an acidic aqueous solution is used in the refining step, higher concentrations (eg, concentrations up to about 100%, preferably about 50%, due to the concentration of non-hydratable phosphatides beyond that removed in the chemical purification step. Acid to a concentration of about 100%). In addition, higher amounts (eg, concentrations up to about 100%, preferably from about 50% to about 100%) of bleaching material are used.

  Prior to bleaching, citric acid (50 wt% solution) can be added to the refined oil and / or chemically refined oil at a concentration of about 0.01 wt% to about 5 wt%. This mixture can then be heated for about 5 to 60 minutes at a temperature of about 35 ° C. to about 65 ° C. and a pressure of about 1 mmHg to about 760 mmHg.

  Refined oils and / or chemically refined oils are subjected to absorption processes (eg, bleaching) to produce peroxides, oxidation products, phosphatides, keratinoids, chlorophyloids, colorants, metals and the like produced in caustic refining and other processing steps Remove residual soap. The bleaching process involves heating the refined or chemically refined oil under a vacuum of about 0.1 mmHg to about 200 mmHg and then a bleaching material suitable for removing the species (eg, natural earth (commonly known as natural clay or Fuller soil), acid activated soil, activated clay and silicate) and filter aids, which heats the mixture to about 75-125 ° C., and converts the bleaching material to refined oil and / or chemicals Contact the refined oil for about 5-50 minutes. It is advantageous to degas before the bleaching material contacts the refined oil. The amount of bleaching material used is from about 0.25% to about 3%, preferably from about 0.25% to about 1.5%, more preferably from about 0.5% to about 1% by weight. . After heating, the bleaching oil or refined bleaching oil is filtered and deodorized.

  The bleaching oil or refined bleaching oil is deodorized to remove compounds with intense odor and flavor and residual free fatty acids. Furthermore, the color of the oil can be decolorized by heating and bleaching at an elevated temperature. Deodorization includes a variety of technologies including batch and continuous deodorization units such as batch stirred tank reactors, liquid film flow evaporators, liquid film evaporators with wipers, packed column deodorizers, tray deodorizers and loop reactors. You can do it. Typically, continuous deodorization is preferred. Generally, deodorization conditions are performed at about 160 to about 270 ° C. and about 0.002 to about 1.4 kPa. With regard to the continuous process, particularly in a continuous deodorizer with a continuous tray for crossing oil, a residence time of up to 2 hours at a temperature of about 170 ° C. to about 265 ° C .; a temperature of about 240 ° C. to about 250 ° C. A residence time of up to about 30 minutes is preferred. Deodorizing conditions can use a carrier gas for removal of volatile compounds (eg, nitrogen, argon, or any other gas that does not reduce the stability or quality of the oil).

Furthermore, if physical purification rather than chemical purification is used, more of the FFA is removed during the deodorization step and the deodorization conditions are modified to facilitate the removal of free fatty acids. For example, the temperature can be increased by about 25 ° C; the oil can be deodorized at a temperature in the range of about 165 ° C to about 300 ° C. In particular, the oil can be deodorized at temperatures ranging from about 250 ° C to about 280 ° C or from about 175 ° C to about 205 ° C. Furthermore, the oil residence time in the deodorizer is extended to about 100%. For example, the residence time can range from about 1, 5, 10, 30, 60, 90, 100, 110, 120, 130, 150, 180, 210 or 240 minutes. The deodorizing pressure is about 3 × 10 ⁻⁴ , 1 × 10 ⁻³ , 5 × 10 ^−3, 0.01 ^, 0.02 ^, 0.03 ^, 0.04 ^, 0.05 ^, 0.06, 0 It can be reduced to less than 0.07, 0.08, 0.09, or 0.1 kPa. The deodorization step results in refined bleach deodorization (RBD) oil.

  If desired, the RBD oil can be stabilized by partial curing and / or by addition of stabilizers or by minimizing the removal or degradation of microcomponents that help maintain oil stability and quality. Can be Partial curing stabilizes the oil by reducing the number of fatty acid double bonds contained in the oil, thus reducing the chemical reactivity of the oil. However, partial curing increases the concentration of undesirable trans-fatty acids.

  Stabilizers generally act to trap free radicals generated during oxidation. Free radical scavenging by stabilizers makes free radicals more stable or rearranges into stable molecules, reducing the concentration of highly reactive free radicals that oxidize more fatty acid units This delays the oxidation of the oil.

  For each of the above Steps in Section II, each step optionally minimizes exposure to oxygen, optionally minimizes heat exposure, minimizes exposure to UV light, and optionally prior to processing. During or after, a stabilizer was added to the seed meat or seed oil. An improvement of these or other methods for preparing the oils of the present invention is entitled “Processes for Preparation of oil components” and was filed on Nov. 4, 2005, with agent number MTC6921.201 (38-21). (53354C)), which is described and exemplified in U.S. Patent Application No., which is expressly incorporated by reference in its entirety.

III. Handling and storage of oil compositions In general, when storing oil compositions, it is advantageous to minimize further oxidation of fatty acids. One oxidation reactant is singlet oxygen, which is generated by light and a photosensitizer. Singlet oxygen reacts many times faster than triplet oxygen. Thus, one way to minimize further oxidation is to store the oils in a dark or substantially opaque container, preferably keeping them at a moderate temperature in the presence of an inert gas. . Preferably, the oil is paired with storage conditions and / or stabilizers and has stable properties that inhibit conversion of the flavor, odor, color, etc. of the oil.

  The oil composition described in Section I typically has advantageous storage stability. For example, in one embodiment, a method of maintaining the storage stability of an oil during shipping or storage includes the oil described in Section I in a container at a temperature in the range of about 4 to about 45 ° C. for at least 1 month. Where the oil has an anisidine value of less than 3 after storage. In another embodiment, a method of maintaining the storage stability of an oil during shipping or storage includes storing the oil in a container at a temperature in the range of about 4 to about 45 ° C. for at least 1 month. Where the absolute change in the anisidine value of the oil during storage is about 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7,. 8, 0.9, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10, 11, 12, 13, No more than 14, 15, 16, 17, 18, 19 or 20. Further, the oil can be stored in an oxygen-free atmosphere or a reduced oxygen atmosphere. Preferably, the oil can be stored at about room temperature; preferably, the oil can be stored at about room temperature for about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 months or more. Alternatively, the oil can be stored for at least one month under refrigeration; moreover, the oil can be stored for at least about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 months or more under refrigeration. In another embodiment, the oil is derived from sources other than marine oils such as fish, seaweed or krill. In a further embodiment of the method of this section, the oil is derived from vegetable oils other than blackcurrant oil, borage oil, echium oil, evening primrose oil, gooseberry oil, hemp oil, or redcurrant oil.

  The method described in Section III can include adding a stabilizer to the oil before or during storage. This stabilizer may comprise at least one complexing agent or at least one antioxidant. In one exemplary embodiment, the stable household comprises citric acid, TBHQ, ascorbyl palmitate, propyl gallate, or derivatives or combinations thereof.

IV. Foods A food product comprising any one of the oil compositions described in Section I can be prepared. In particular, edible compositions include spray-dried or freeze-dried food particles, an extruded food, meat products, fake meat, cereal products, snack foods, baked good, health foods, fried foods. (fried food), dairy products, simulated cheese, simulated milk, pet food, food including feed or aquaculture feed or food analog. In another embodiment, the food is a beverage; the beverage is an adult nutritional formula, an infant formula, juice, milk drink, soy milk, yogurt drink, It can be a smoothie or a reconstituted dry powder such as a non-dairy creamer. In addition, foods include nutritional supplements, spreads, margarines, salad dressings, cooking oils, a refrigerated dough product, microwave popcorn, yogurt, cheese, cream cheese, sour cream or mayonnaise dairy products, bread, rolls, It may be a cake, pastry, cookie, muffin or baked good, appetizer, side dish, soup, sauce, granola, cereal, snack bar, nutrition bar, or confectionery.

  One advantage of oils containing 4 or more double bonds produced by the process of the present invention is that they are non-irritating with respect to taste and odor. They can also be stored for a period of time at room temperature while maintaining their flavor and sensory identity. Furthermore, it has the advantage that it can be stored in refrigerated conditions while still maintaining no irritation. These oils can be encapsulated or frozen by methods well known in the art for fish oil stabilization.

  Having described the invention in detail, it will be apparent that modifications and variations are possible without departing from the scope of the invention as defined in the appended claims. Further, all examples disclosed herein are to be understood as non-limiting examples.

Example 1: Accelerated aging of oil Polyethylene glycol solutions of each stabilizer were prepared. The solution was vortexed at high speed for 5 minutes. In a nitrogen-substituted glove box, an appropriate amount of each solution was added to 2.5 g (2.77 mL) test oil in a 60 cc glass brown bottle with a Teflon lid to obtain a mixture. These mixtures were then vortexed at high speed for 1 minute. A portion of these mixtures was then removed with a plastic pipette and placed in a brown vial.

  An untreated oil additive sample was also prepared as described above (without the addition of a stabilizer). Each stabilizer was added at the following concentrations: citric acid (CA) 50 ppm, ascorbyl palmitate (AP) 400 ppm, and t-butylhydroquinone (TBHQ) 120 ppm.

  The vial (containing untreated oil and oil with added stabilizer) was then opened in air to fully replace the vial headspace. The vial was again capped and heated to 55 ° C. in a water bath. Samples were removed and peroxide values were measured at different time intervals. In general, aging of a sample stored at 55 ° C. for 1 day corresponds to aging of a sample stored at room temperature (about 20-25 ° C.) for about 10 days. 20% by weight SDA, entitled “Processes for Preparation of oil components”, filed on Nov. 4, 2005, with US Patent Application No. MTC6921.201 (38-21 (53354C)) Test oils prepared using the process conditions of Examples 45 and 46 described were aged using the protocol described above. The results of this aging experiment are presented in the graph of FIG. Three oils with a single additive (CA, AP, and TBHQ) and two oils with two additives (CA + AP and CA + TBHQ) were evaluated. Citric acid-containing SDA oil shifted from the initial phase (IP) to the growth phase (PP) after 2 days. FIG. 1 shows a plot of AV versus time. This plot shows longer IP (about 8 days) for ascorbyl palmitate added oil and longer IP (about 10 days) for TBHQ added oil compared to CA added oil. TBHQ additive oil was the best single additive stabilizer for this particular oil.

  FIG. 1 also shows the oxidation of oil with AP and CA addition and TBHQ and CA addition. AP and CA added oils showed shorter IPs compared to AP only added oils. TBHQ and CA-added oil showed the longest IP among the oils tested in this experiment.

Example 2: Aging experiments at 55 ° C and 25 ° C The oils included in this experiment are: 20% SDA test article (TA) processed on experimental scale and pilot scale (PS); equivalent and SDA negative (Example 45 described in US Patent Application No. MTC6921.201 (38-21 (53354C)) filed Nov. 4, 2005, entitled “Processes for Preparation of oil components” and No additive) prepared with 46 process conditions; and Soybean Control Oil 1. In addition, a 4% SDA oil blend was prepared by blending 20% SDA oil with Soybean Control Oil 1 or no additive oil. The relative ranking in the stability of these oils based on PV and AV vs. time at 55 ° C is from TA-Lab <TA- (PS) <CA TA-PS <CA TA- Lab << 4% blend with CA (TA-PS additive-free) <4% blend with CA (TA-PS plus soybean control oil 1) <additive-free <soybean control oil 1 (see Figure 2) . The relative ranking of stability was determined by comparing the time when the PV or AV value crosses 10. In general, this is the point where the transition from the start phase to the growth phase begins. At 25 ° C. (see FIG. 3), five oils transitioned from the onset to the growth phase (by AV), which is clearly qualitative and quantitative relative to the data obtained at 55 ° C. The position was the same.

  Another accelerated aging test at 55 ° C. was performed using 20% SDA test article with citric acid (50 ppm), ascorbyl palmitate (400 ppm), and TBHQ (120 ppm). One sample contained a mixture of all three stabilizers in these amounts. In addition, commercial fish oil products such as fish oil 3 (with TBHQ and tocopherol) and fish oil 4 (with ascorbyl palmitate and tocopherol) were included as controls. To further evaluate these commercial fish oil products, they were blended with Soybean Control Oil 1 to make SDA oil and EPA + DHA bioequivalent. One EPA molecule is generated for all three SDA molecules consumed. Thus, if EPA, DPA, and DHA are comparable in bioefficiency, to produce the same amount of EPA, three times more SDA than EPA must be consumed. The total omega-3 fatty acids were quantified for each fish oil and each oil was diluted to a 6.67 wt% solution with soybean oil so that it could be compared directly to a 20 wt% SDA oil. FIG. 4 shows the AV versus time for these oils. Initial AV results show that 20% SDA oil stabilized with AP, TBHQ, and a combination of AP, TBHQ, and CA contains a biologically equivalent dilution and has a longer onset than Fish Oil 3 and Fish Oil 4. It shows that.

Example 3 IR Thin Film Oxidation Experiments Methods for accelerated aging and oxidative stability evaluation of oils are described in McGill University [J. Am. Oil. Chem. Soc, 2003, 80, 635-41; J. Am. Oil. Chem. Soc, 2004, 81, 111-6] was adopted. This method was employed to protect the oil from air during preparation and ensure a constant film thickness. An oil film was prepared on a PTFE film (polytetrafluoroethylene such as Teflon ^R ) mounted on a rectangular cardboard card that can be easily mounted on an IR spectroscopic analyzer. Cards were purchased from International Crystal Laboratories, Garfield, NJ, part no. 0006-7363.

  The oil composition for the test was prepared under argon in a glove box. Typically, 0.2-0.5 g is placed in a vial, which is then sealed and removed from the dry box. At least two infrared cards were labeled for each sample and spread over tissue to prevent contamination. A thick layer of oil was then applied to the labeled card using an artificial fiber (not camel hair) brush. Since the Teflon support film is cracked, some oil soaked into the support tissue. In order to avoid excessive air exposure, the card was then immediately spread flat into a new tissue in the box. The box was transferred to a vacuum chamber where it was immediately degassed and filled with argon. The box containing the card was left in the chamber overnight in the dark. During this time, excess oil soaked into the tissue produced a constant thickness oil film.

The next day, an infrared spectrum of each card was acquired using a Nicolet Model 550 Fourier Transform Infrared Spectrometer controlled by the Nicolet's Omnic software package, version 4.1b. The curd was then stood and placed in a 60 ° C. oven, taking care that the oil film did not touch the source of contamination. Other temperatures can be used, but for oils rich in PUFA, a temperature of 60 ° C. produces an oxidation rate that allows the oxidation curve to be measured sufficiently accurately in one spectrum per day. Typically, the infrared spectrum of the oil film was acquired daily and scanned 32 times over the spectral range 400-4000 cm ⁻¹ . This spectral range was wider than the region of interest and was used because a wider baseline was obtained. After spectrum acquisition, baseline correction was performed using "Automatic Baseline Correction" of Omnic Software. When the oil was oxidized, a broad peak at 3400 cm ⁻¹ became larger; it was attributed to absorption of OH stretching within the peroxide group. Decay in the absorption of C—H stretching associated with the cis carbon-carbon double bond at 3011 cm ⁻¹ was also observed and useful for confirmation, but quantification of the degree of oxidation was achieved by integration of the peroxide peak.

For the quantification of the peroxide peak, the film thickness is proportional to the absorption of the CH2 stretching peak at 2900 cm ⁻¹ . By placing the card horizontally on the tissue overnight, an oil film with an absorption between 0.2 and 0.6 where the highest energy of the two CH2 stretching peaks is generally obtained. In order to compare the spectra on a constant basis, the spectra were normalized after baseline correction and prior to integration so that this peak had an absorption of 1.0. Once the highest energy CH2 stretching peak was normalized, then the peroxide peak was integrated. The entire peak was not integrated to compensate for baseline bending. Optimization integration parameters to be used for all data and calibration below presented herein is the integral range of 3583cm ^-1 from a base line and 3251cm ^-1, which is integrated in 3222~3583cm ^-1.

  The above method is corrected as follows. A series of peroxide value standards were prepared by mixing oxidized Wesson soybean oil and Wesson soybean oil from a fresh bottle. The oxidized oil was prepared by placing 126 g Wesson soybean oil in a 250 mL round bottom flask and adding 44 mg iron (II) stearate. The oil was vented overnight (16 hours) in a 90 ° C. oil bath. The oil turned yellowish brown. The final weight of the oil was 128g. Some iron stearate did not dissolve and adhered to the flask, but was removed when the oil was transferred. Titration measurements showed that the oxidized oil had a PV of 680 meq / kg and the fresh Wesson soybean oil had a PV of less than 0.1 meq / kg. A calibration standard was prepared using a mixture of two oils and analyzed as described above.

This method is only used to quantify the change in peroxide value from the first sample. here,
ΔPV (meq / kg) = Δ area × 228.4
[Where ΔPV is the change in peroxide value and Δ area is the change in peak area, reported by Omnic Software. ] Was found.

Using the above protocol, relative to the oxidation of the oil of the present invention with the addition of a stabilizer selected from ascorbyl palmitate (AP), propyl gallate (PG), t-butylhydroquinone (TBHQ) and combinations thereof Stability was quantified. In these experiments, it was found that the other stabilizers were not as effective in delaying the oxidation of the test oil as the above stabilizers, ie other stabilizers were not allowed to be used in food. . These low-efficiency or non-food-compatible stabilizers are: Carotino ^R from Carotino, SDN, BDH (mixture of tocotrienols and carotenes), phenanthroline, pentaethylenehexaamine (PEH), diethanolamine (DEA), butylated Hydroxytoluene (BHT), and combinations thereof.

  These studies used the thin film IR method to show that the order of effectiveness of stabilizers or stabilizer combinations is (AP + PG)> AP> PG> TBHQ-untreated oil. This order is somewhat different from the accelerated aging data of Examples 1 and 2. This is because TBHQ has been found to be a very effective stabilizer in conventional aging experiments, but because of the exposure conditions of the oil film, the oxidation of the film is probably not the oxidation of a large amount of oil. It has been confirmed that it receives a different mechanism. For example, thin film oil oxidation at 60 ° C. will be closer to the high temperature oxidation of the oil, thus giving results closer to the results of the OSI data. In order to confirm this hypothesis, an OSI experiment was conducted on an oil to which a stabilizer was added. The OSI protocol is described in detail above, and one method for quantifying OSI values is AOCSCd12b-92.

  The OSI values for 20% SDA soybean oil containing stabilizers are shown in the table below. Most samples were evaluated twice.

  As observed from the OSI data, the order of validity is the same as the OSI data of the thin film IR data. Representative thin film IR data for a 20% SDA oil composition with PG and AP added is shown in FIG.

Example 4
AV lowering resin A sample of SDA canola oil with AV = 5.41 was used to confirm the idea that certain resins reduce the AV value in the oil. A small amount of “Wheaton type” RBF was added to 10 g of oil and connected to a device that could be evacuated. For each experiment, 1 gram of resin was added to the oil. Resin # 1 was 2- (4-toluenesulfonylhydrazine) -ethyl-functionalized silica gel, 200-400 mesh (Aldrich 552593-25g). Resin # 2 was 3-aminopropyl-functionalized silica gel (Aldrich 36,425-8). The mixture was then degassed in a system under vacuum. The oil was then lowered into a 110 ° C. oil bath and mixed with a stir bar for 1 hour. The mixture was cooled and filtered through 0.2 μm acrodisc ^R for analysis. Experiment 1 was repeated to obtain two AV values.

Example 5
The purpose of the aroma experiment (Sensory Test 1) was to characterize the aroma of SDA enriched soybean oil. As a reference framework, processed control soybean oil (no added seed oil), as well as some commercial soybean oils and the aroma of omega-3 containing fish and seaweed oils were also tested.

  The purpose of the aroma / taste / feel test (sensory test 2) was to characterize the aroma, taste and feel of SDA enriched soybean oil. As a reference framework, the aroma, taste and texture of omega-3 containing processed control soybean oil (no added seed oil) and several commercial soybean oils and fish and seaweed oils were also tested.

The following test oil, control oil and Comparative oils were evaluated spectrum ^{R (Spectrum R)} using a standardized sensory evaluation.
Test oil 1 is 15% SDA-enriched RBD soybean oil (LGNBP739406615BJ9); Test oil 2 is 15% SDA-enriched RBD soybean oil (LLNBP739406915CK1); Test oil 3 is 20% SDA-enriched RBD soybean oil (LMNBP739406920AQ6) Test oil 4 is 20% SDA-enriched RBD soybean oil (LHNBP739406920BJ7); Test oil 5 is 20% SDA-enriched RBD soybean oil (LEGLP050115725SN5); Test oil 6 is 20% SDA-enriched RBD soybean oil (LTAGT050115759SN3); Test oil 7 is equivalent control RBD soybean oil (LMAGT050115757SU0); Test oil 8 is 15% SDA-enriched RBD soybean oil (LC739406615BX1); Test oil 9 is 21% SDA-enriched RBD soybean oil (LZAGT050115759SJ9); Oil 10 is 17% SDA-enriched RBD soybean oil with citric acid (LHAGT050716475SO3); Test oil 11 is 17% SDA-enriched RBD soybean oil with citric acid (LLAGT050716477SY1); and Test oil 12 is 1 with citric acid % SDA- is enriched RBD soybean oil (LEAGT050716481SU5). Control oil 1 is RBD soybean oil from pooled additive (LGAGT050115757SU9); Control oil 2 is RBD soybean oil from pooled additive without citric acid (LNAGT050716474SW4); and Control oil 3 is pooled without citric acid RBD soybean oil (LMAGT050816495SL7) from additive.

  For sensory test 1, the composition of the oil used for comparison is shown in the table below. Soybean oil 1 is a commercially produced soybean oil; Soybean oil 2 is another soybean oil produced commercially; Soybean oil 3 is another soybean oil produced commercially; Fish oil 1 is commercially available Manufactured fish oil; flax oil 1 is commercially manufactured flax oil; seaweed oil 1 is commercially manufactured seaweed oil; and seaweed oil 1 is commercially manufactured Another seaweed oil.

  For sensory test 2, the composition of each comparative oil is listed in the table below. Comparative oil 1 is a commercially produced RBD soybean oil; comparative oil 2 is a commercially produced RBD soybean oil; comparative oil 3 is a commercially produced fish oil; comparative oil 5 is produced commercially. Comparative oil 6 is a commercially produced fish oil; comparative oil 7 is a commercially produced seaweed oil; and comparative oil 8 is a commercially produced seaweed oil.

  All test and control oils were sealed in 200-1000 mL brown glass bottles with screw caps. Test and control oils were wrapped with nitrogen and frozen immediately after processing. Test and control oils were not opened during storage. The comparative oil is obtained from a commercial manufacturer and remains in its original package. Stored at 5 ° C or -20 ° C as per manufacturer's support.

Spectrum ^{TM (Spectrum TM)} were evaluated oil using descriptive analysis ^{(reference: [Sensory Evaluation Techniques, 3 rd} ed .; Meilgaard, Morten; Civille, GailVance .; Carr, B. Thomas; CRC Press LLC, New York, 1999; ISBN 0-8493-0276-5]). The test panel consisted of 6-8 people trained in oil evaluation. All panelists were swapped together for each test session. After warming to room temperature, ½ to 1 ounce aliquots were presented for evaluation.

  Each product was evaluated by all panelists at once. Using a common rating for scores from 0 (not detected) to 15 (extreme), the panelists ranked and discussed each of the total impact as well as the detected sensory attributes. For each of the total impacts and descriptions, the rankers moved to sensory voting by the experimental director. Aromatic attributes include, but are not limited to, fish / swamp complex, fish, swamp, protein / fertilizer, paint, beans, fermentation, floral, nuts, cardboard, greens, grass, weeds, vegetable oil, corn shaft, and phenol / plastic including. Taste attributes are not limited, but fish / swamp complex, fish, swamp, protein / fertilizer, paint, beans, fermentation, floral, nuts, cardboard, greens, grass, weeds, vegetable oil, corn, albumin, seeds / nuts / Includes pumpkin and phenol / plastic. The basic tastes were rated on a scale of 0 to 15 for the sweet, sour, salty and bitter attributes. Chemical quality was ranked with a score of 0 to 15 for the attributes of astringency, scorching, and chemical quality. The touch was ranked with a score of 0 to 15 per stickiness. The aftertaste was not ranked but was observed and listed.

  Test oils 10 to 12 and control oils 2 and 3 were fresh oils; they were processed to the RBD stage within 2 months before the start of the experiment. These oils were tested in the first test session of the experiment. Test oils 8 and 9 were evaluated as part of the low temperature storage stability test. Test oil 8 was processed about one year before the test and stored at -80 ° C until the start of the test. This oil was tested in the first test session of the experiment. Test oil 9 and control oil 1 were processed about 6 months before the start of the experiment and stored at -20 ° C. This oil was tested in the first test session of the experiment. There are no further samples tested as part of the cold storage stability test.

  The accelerated stability test sample was stored at 55 ° C. in a constant temperature incubation oven (sensory test 1). The storage stability test samples were stored in a constant temperature incubation oven at 15 ° C.

  The table below shows data for the fragrance only test (sensory test 1).

  The table below shows data for the aroma / taste / feel test (sensory test 2).

Example 6: Mayonnaise Preparation Soybean oil (3720 g) and omega-3 vegetable oil (1800 g) were blended to give the following oil composition:
Free fatty acid,% 0.35
Peroxide value 0.09
Color 1.3Y 0.0R
Chlorophyll, ppm 0.00
Anisidine value 0.20

Fatty acid composition,%
C14 (Myristic acid) 0.04
C16 (palmitic acid) 11.15
C16: 1n7 (palmitooleic acid) 0.11
C18: 0 (stearic acid) 4.58
C18: 1n9 (oleic acid) 20.24
C18: 1 (octadecenoic acid) 1.36
C18: 2n6 (linoleic acid) 45.17
C18: 3n6 (gamma linolenic acid) 3.00
C18: 3n3 (alpha linolenic acid) 3.41
C18: 4n3 (octadecatetraenoic acid) 3.21
C20: 3n6 (dihomogamma linolenic acid) 0.05
C20: 4n6 (arachidonic acid) 0.20
C20: 5n3 (eicosapentaenoic acid) 2.95
C22: 6n3 (docosahexaenoic acid) 1.96
C20 (Arachidonic acid) 0.35
C20: 1n9 (eicosenoic acid) 0.15
C22 (behenic acid) 0.32
C24 (Lignoceric acid) 0.12
Other 1.64

  In addition to the above oil blend, the following ingredients were used to make mayonnaise: vinegar (6300 g), egg ingredient (720 g), water (3000 g), and salt (1300 g). The top space of all blend containers was wrapped with nitrogen. An emulsified dressing was then made by dispersing the eggs in 240 g of water. Then, salt was added. This was stirred rapidly. The remaining water and vinegar were added and the loose emulsion passed through a colloid mill (such as a Fryma mill). The resulting mixture was pH 4.0. The resulting product had mayonnaise characteristics and stability. With the product obtained. Turkey sandwiches, coleslaw and potato salads were made. The finished product was indistinguishable from mayonnaise made in oil that did not contain any fatty acids with more than 4 double bonds in the test.

FIG. 1A is a graph of peroxide value (PV) versus time for an oil composition containing 20 wt% stearidonic acid (SDA) and various stabilizers added. The graph of FIG. 1 shows the results of an accelerated aging test performed at 55 ° C. FIG. 1B is a graph of anisidine value (AV) versus time for an oil composition containing 20 wt% stearidonic acid (SDA) and various added stabilizers. The graph of FIG. 1 shows the results of an accelerated aging test performed at 55 ° C. FIG. 2A is a graph of PV versus time for a 20% SDA, 4% SDA blend, 20% SDA containing citric acid and a control soybean oil composition. The graph of FIG. 2 shows the results of an accelerated aging test performed at 55 ° C. FIG. 2B is a graph of AV versus time for a 20% SDA, 4% SDA blend, citric acid with 20% SDA and a control soybean oil composition. The graph of FIG. 2 shows the results of an accelerated aging test performed at 55 ° C. FIG. 3A is a graph of PV versus time for a 20% SDA, 4% SDA blend, 20% SDA containing citric acid and a control soybean oil composition. The graph of FIG. 3 shows the results of a room temperature aging test performed at 25 ° C. FIG. 3B is a graph of AV versus time for a 20% SDA, 4% SDA blend, citric acid with 20% SDA and a control soybean oil composition. The graph of FIG. 3 shows the results of a room temperature aging test performed at 25 ° C. FIG. 4 is a graph of AV versus time for 20% SDA, citric acid with 20% SDA, commercial fish oil, and a bioequivalent SDA blend oil composition. The graph of FIG. 4 shows the results of an accelerated aging test performed at 55 ° C. FIG. 5 is a graph of peroxide value (PV) versus time for a 20% SDA oil composition containing 200 ppm ascorbyl palmitate and 0, 30, 60, and 120 ppm propyl gallate. FIG. 5 shows the results of an accelerated aging test performed at 60 ° C. using thin film IR. FIG. 6A shows (i) ascorbyl palmitate (AP) and TBHQ, (ii) citric acid (CA) and ascorbyl palmitate (AP), and (iii) citric acid (CA), TBHQ, and ascorbyl palmitate ( 2 is a graph of peroxide value (PV) versus time for a 20% SDA oil composition containing (AP). FIG. 6B shows (i) ascorbyl palmitate (AP) and TBHQ, (ii) citric acid (CA) and ascorbyl palmitate (AP), and (iii) citric acid (CA), TBHQ, and ascorbyl palmitate ( FIG. 2 is a graph of anisidine value (AV) versus time for a 20% SDA oil composition containing (AP).

Claims (9)

A refined, bleached and deodorized soybean oil composition comprising from 3 to 30 % by weight of stearidonic acid or a derivative thereof relative to the total weight of fatty acids or derivatives thereof in the composition , wherein said soybean oil The soybean oil composition having an anisidine value of less than 3 other than soybean oil having stearidonic acid added to the composition.   The soybean oil composition of claim 1, wherein the composition has a peroxide value of less than 1 meq / kg. 2 or more include a polyunsaturated fatty acid or derivative thereof, having a anisidine value of less than 3, soybean oil composition according to claim 1 having a carbon double bond - et al 4 or more carbon is.   The soybean oil composition according to claim 1, wherein the composition is a genetically modified soybean oil.   The soybean oil composition of claim 1, wherein the composition has an aroma total impact score of up to 2.5, wherein the total impact is determined by a standardized sensory evaluation.   The soybean oil composition of claim 1, wherein the composition has an aroma / flavor total impact score of up to 2.5, wherein the total impact is determined by standardized sensory evaluation. Fatty acid or including a 10-30 wt% of the stearidonic acid or a derivative thereof based on the total weight of the derivative in the composition, soy oil composition according to any one of claims 1 to 6. A food, beverage, nutritional supplement or cooking oil comprising the soybean oil composition according to any one of claims 1 to 7 . The soybean oil according to any one of claims 1 to 8 , further comprising a stabilizer selected from the group consisting of citric acid, t-butylhydroquinone, ascorbyl palmitate, propyl gallate, and combinations thereof. Composition, beverage, nutritional supplement or cooking oil.

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